CN104610056B - Compound, catalyst solid composition containing compound, and catalyst - Google Patents
Compound, catalyst solid composition containing compound, and catalyst Download PDFInfo
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- CN104610056B CN104610056B CN201310535348.6A CN201310535348A CN104610056B CN 104610056 B CN104610056 B CN 104610056B CN 201310535348 A CN201310535348 A CN 201310535348A CN 104610056 B CN104610056 B CN 104610056B
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Abstract
The invention discloses a compound with a novel structure. Structural formula of the compound is represented by formula (1), wherein R1, R2, R3, and R4 may be used for representing the same groups or different groups, and are independently selected from substituted or unsubstituted C1-C20 alkyl groups, and are optimally selected from substituted or unsubstituted C1-C10 aliphatic hydrocarbon groups, C3-C10 naphthene grous, C6-C20 aryl groups, and C7-C20 alkaryl groups, and R3 and R4 can be randomly connected to obtain a ring or no rings. The compound represented by formula (1) can be taken as an internal electron donor compound; a catalyst with excellent comprehensive properties can be obtained; when the compound is used for olefin polymerization, polymerization activity is high, stereotactic performance is excellent, and obtained polymers are high in isotacticity and melt index.
Description
Technical field
Present invention relates particularly to a kind of compound of new structure, with the catalysis that the compound is obtained as internal electron donor
Agent component and the catalyst containing the catalyst component.The invention further relates to catalyst application in olefin polymerization.
Background technology
The catalyst constituted as the solid titanium catalyst component of basis using magnesium, titanium, halogen and internal electron donor, i.e.,
Ziegler-Natta catalyst known in the field, can be used for CH2The polyreaction of=CHR alkene, particularly with 3
The polymer of higher yields and higher stereospecificity can be obtained in the alpha-olefine polymerizing of carbon or more carbon atoms.Many institute's weeks
Know, Donor compound is one of requisite composition in Ziegler-Natta catalyst component.From early stage disclosed unitary
Carboxylic acid ester compound, such as ethyl benzoate, binary aromatic carboxylic acid's ester type compound widely used up till now, such as adjacent benzene
Dioctyl phthalate di-n-butyl or o- benzoic acid diisobutyl ester, then to the recent disclosed ethers of 1,3- bis-（CN1020448C）, succinic acid
Esters（CN1313869）With 1,3- diol-lipids（CN1213080C）The development of compound, exactly internal electron donor compound is led
Polyolefin catalyst has been caused to be continuously updated the replacement.
With the continuous progress of catalyst research, it is desirable to new internal electron donor is found, so as to obtain having more preferably
The catalyst of combination property, to meet the needs of olefinic polymerization development.
The content of the invention
For deficiency of the prior art, the present inventor is passed through deep experimentation, there is provided a kind of new structure
Compound, it can be used as catalyst solid constituent（Or title catalytic component）Internal electron donor compound, and comprising described
The catalytic component and catalyst of compound.The catalyst solid constituent and catalyst provided according to the present invention is poly- for alkene
Close, have the advantages that catalysis activity is good, stereoselectivity is good, isotacticity is high, high melt index and hydrogen regulation performance are good.
According to an aspect of the present invention, the invention provides a kind of compound of new structure, its structural formula such as following formula
（I）It is shown：
In formula, R1、R2、R3And R4Can be identical or differ, be each independently selected from substituted or unsubstituted C1-C20Hydrocarbon
Base, is preferably selected from substituted or unsubstituted C1-C10Aliphatic group, C3-C10Cycloalkyl, C6-C20Aryl and C7-C20Alkane
Aryl;R3And R4Cyclization or not cyclization can arbitrarily be connected.
According to the present invention, the substituted C1-C10Alkyl, C6-C20Aryl and C7-C20Alkaryl etc. replace
Group, refers to if the hydrogen atom on phenyl ring in the alkyl, aryl or alkaryl is optionally by halogen（It is miscellaneous）Atom, alkyl or
Alkoxyl replaces, and the carbon atom on the main chain is optionally exchanged for heteroatoms.In the present invention, the aliphatic group can be straight
Chain or branched structure, include alkyl and undersaturated group such as thiazolinyl of saturation etc..The hetero atom selected from nitrogen, oxygen, sulfur,
Silicon, phosphorus or halogen atom etc..
A specific embodiment of the invention, the R1And R2Group is selected from substituted or unsubstituted C1-C10Fat
Alkyl, C3-C10Cycloalkyl and C6-C20Aryl；It is preferred that R1And R2Group is substituted or unsubstituted C1-C6Alkyl, such as
May include methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, pi-allyl etc..
Another specific embodiment of the invention, the R3And R4Group is selected from substituted or unsubstituted C1-C10Fat
Fat alkyl, C3-C10Cycloalkyl and C6-C20Aryl；It is preferred that R3And R4Group is selected from substituted or unsubstituted C1-C6Hydrocarbon
Base and C6-C12Aryl, such as may include methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, pi-allyl, benzene
Base, benzyl etc..
Catalytic component in the present invention, for described formula（I）Shown compound, suitable examples of compounds
It is selected from, but not limited to,：Double (acetoxyl group the methylene) -1,3- dimethoxy propanes of 2,2-, 2,2- double (propionyloxy methylene) -
Double (butyryl acyloxy the methylene) -1,3- dimethoxy propanes of 1,3- dimethoxy propanes, 2,2-, 2,2- are double, and (isobutyl acyloxy is sub-
Methyl) -1,3- dimethoxy propanes, double (valeryl epoxide the methylene) -1,3- dimethoxy propanes of 2,2-, double ((the 1- first of 2,2-
Base) butyryl acyloxy methylene) -1,3- dimethoxy propanes, double (isoamyl acyloxy the methylene) -1,3- dimethoxys third of 2,2-
Double (double (hexylyloxy the methylene) -1,3- diformazans of (pivaloyl epoxide methylene) -1,3- dimethoxy propanes, 2,2- of alkane, 2,2-
Double ((1- methyl) valeryl epoxide the methylene) -1,3- dimethoxy propanes of epoxide propane, 2,2-, double ((2- methyl) valeryls of 2,2-
Epoxide methylene) -1,3- dimethoxy propanes, double (dissident's acyl-oxygen methylene) -1,3- dimethoxy propanes of 2,2-, 2,2- be double
Double (special hexylyloxy the methylene) -1,3- two of ((1,1- dimethyl) butyryl acyloxy methylene) -1,3- dimethoxy propanes, 2,2-
Double ((1,2- dimethyl) butyryl acyloxy the methylene) -1,3- dimethoxy propanes of methoxy propane, 2,2-, the double (acrylyls of 2,2-
Epoxide methylene) -1,3- dimethoxy propanes, double (benzoxy the methylene) -1,3- dimethoxy propanes of 2,2-；It is preferred that selecting
From double (acetoxyl group the methylene) -1,3- dimethoxy propanes of 2,2-, double (propionyloxy the methylene) -1,3- dimethoxys of 2,2-
Double (butyryl acyloxy the methylene) -1,3- dimethoxy propanes of propane, 2,2-, double (isobutyl acyloxy the methylene) -1,3- two of 2,2-
Double (valeryl epoxide the methylene) -1,3- dimethoxy propanes of methoxy propane, 2,2-, 2,2- double (isoamyl acyloxy methylene) -
1,3- dimethoxy propanes, 2,2- are double, and ((pivaloyl epoxide methylene) -1,3- dimethoxy propanes, 2,2- are double, and (hexylyloxy is sub-
Methyl) -1,3- dimethoxy propanes, double (dissident's acyl-oxygen methylene) -1,3- dimethoxy propanes of 2,2-, 2,2- it is double (it is special oneself
Acyl-oxygen methylene) -1,3- dimethoxy propanes, double ((1,2- dimethyl) butyryl acyloxy the methylene) -1,3- dimethoxies of 2,2-
Double (allyl acyloxy the methylene) -1,3- dimethoxy propanes of base propane, 2,2- and double (the benzoxy methylenes) -1 of 2,2-,
3- dimethoxy propanes；It is more preferably selected from double (acetoxyl group the methylene) -1,3- dimethoxy propanes of 2,2-, the double (propionyl of 2,2-
Epoxide methylene) -1,3- dimethoxy propanes, double (butyryl acyloxy the methylene) -1,3- dimethoxy propanes of 2,2-, 2,2- be double
Double (valeryl epoxide the methylene) -1,3- dimethoxy propanes of (isobutyl acyloxy methylene) -1,3- dimethoxy propanes, 2,2-,
Double (isoamyl acyloxy the methylene) -1,3- dimethoxy propanes of 2,2-, double ((pivaloyl epoxide the methylene) -1,3- diformazans of 2,2-
Double (hexylyloxy the methylene) -1,3- dimethoxy propanes of epoxide propane, 2,2-, double (the dissident's acyl-oxygen methylenes) -1 of 2,2-,
Double (special hexylyloxy the methylene) -1,3- dimethoxy propanes of 3- dimethoxy propanes, 2,2-, 2,2- are double, and (benzoyloxy is sub-
Methyl) -1,3- dimethoxy propanes.
According to the compound that the present invention is provided, it can be prepared by following steps：First synthesize double (the methoxyl group methylenes of 2,2-
Base) -1,3-PD, then reacted with corresponding acylating reagent by it, obtain the chemical combination shown in heretofore described Formulas I
Thing（Such as can react with alkyl acyl chloride）.Wherein, double (the methoxymethylene) -1,3-PDs of 2, the 2- can pass through following
Step must be synthesized：Tetramethylolmethane and benzaldehyde are in catalyst（Such as concentrated hydrochloric acid）In the presence of react, obtain being carried out after solid
Solid-liquid separation, is processed solid, purification, obtains 2- ((2- phenyl) -1,3- dioxocyclohex bases) -1,3-PD；Then
2- ((2- phenyl) -1,3- dioxocyclohex bases) -1,3-PDs and the sodium hydride reaction of excess, add excessive dimethyl sulfate
Ester, it is purified after reaction terminates（Such as plus water washing, point liquid, drying, vacuum distillation）Obtain 2- ((2- phenyl) -1,3- two
Oxygen cyclohexyl) -1,3- dimethoxy propanes；Then it is hydrogenated with lower Pd-C catalytic action and obtains double (the methoxyl group methylenes of 2,2-
Base) -1,3- Propylene Glycol.The reaction of above-mentioned steps can be carried out according to selection in suitable solvent.
The compound of the new structure provided according to the present invention, can be used for olefinic polymerization, such as catalyst solid constituent
Internal electron donor, the catalyst for obtaining has good combination property, with broad application prospect.
According to another aspect of the present invention, a kind of catalyst solid constituent for olefinic polymerization is additionally provided（Or
Claim catalytic component, ingredient of solid catalyst）, including titanium, magnesium, halogen and above-mentioned formula（I）Shown compound.
Catalyst according to the invention solid constituent, the titanium（Element）Content be 1.0-8.0wt%, preferably 1.6-
6.0wt%；Magnesium（Element）Content be preferably 10-70wt%, preferably 15-40wt%；Halogen（Element）Content be 20-
85wt%, preferably 30-80%；The formula（I）Shown compound（Internal electron donor compound）Content 2-30wt%, preferred 3-
20wt%。
According to catalyst solid constituent of the present invention, it is magnesium compound, titanium compound and formula（I）Shown chemical combination
Thing product in a solvent.For preparing titanium compound, magnesium compound and the interior electron of the catalyst solid constituent
The consumption of body compound is not particularly limited, and can be respectively the conventional substances and consumption of this area.
In a preferred embodiment, the magnesium compound is selected from formula M gR4R5Shown magnesium compound, formula
MgR4R5·pH2The hydrate and formula M gR of the magnesium compound shown in O4R5·qR6The alcohol adduction of the magnesium compound shown in OH
Thing, in formula, R4And R5It is each independently selected from halogen, C1-C8Straight or branched alkoxyl and C1-C8Straight or branched
Alkyl；P and q are separately selected from 0.1-6, preferred 2-3.5；R6For C1-C18Alkyl, preferably C1-C8Alkyl, it is more excellent
Choosing is selected from methyl, ethyl, n-pro-pyl and isopropyl.For example, the magnesium compound can for dimethoxy magnesium, diethoxy magnesium,
Dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two epoxide magnesium, two (2- second
Base) epoxide magnesium, methoxy magnesium chloride, methoxyl group magnesium bromide, methoxyl group magnesium iodide, ethyoxyl magnesium chloride, ethyoxyl magnesium bromide,
Ethyoxyl magnesium iodide, propoxyl group magnesium chloride, propoxyl group magnesium bromide, propoxyl group magnesium iodide, butoxy magnesium chloride, butoxy bromination
Magnesium, butoxy magnesium iodide, methyl-magnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, amyl group magnesium chloride, phenylchloride
Change magnesium, magnesium dichloride, dibrominated magnesium, magnesium diiodide, the alcohol adducts of magnesium dichloride, alcohol adducts of dibrominated magnesium and diiodinating
At least one in the alcohol adducts of magnesium.Most preferably, the magnesium compound contains diethoxy magnesium, butylmagnesium chloride, ethoxy
At least one in base magnesium chloride, magnesium dichloride.
Preferred at another, the formula of the titanium compound is TiXm(OR7)4-m, in formula, X is halogen, R7For C1-C20
Alkyl, preferred C1-C5Alkyl, m for 0-4 integer.For example：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four butoxy
At least one in titanium, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and the ethanolato-titanium of trichlorine one.It is optimum
Selection of land, the titanium compound is titanium tetrachloride.
In the specific embodiment of the inventive method, catalyst component exemplary is prepared such as by following methods.
Method one, alkoxyl magnesium or Alkoxymagnesium halides is suspended in inert diluent and forms suspension, then this is hanged
Supernatant liquid contacts to obtain solidss dispersion, commonly referred to mother solution with above-mentioned titanium compound, internal electron donor mixing.By mother solution mistake
Filter, gained solid matter is suspended in the solution containing titanium tetrachloride carries out contact process, and commonly referred to titanium is processed；Then pass through
Filter, washing can be prepared by the catalyst solid constituent of the present invention.
As the specific example of above-mentioned alkoxyl magnesium, can enumerate dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium,
Diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, two hexyloxy magnesium, two (2- ethyls) hexyloxy magnesium
Deng or its mixture, the preferably mixture of diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesiums.The alkoxyl magnesium
The preparation method of compound, can be prepared by method well known in the art, as disclosed in patent CN101906017A by magnesium metal with
Fatty alcohol is prepared in the presence of a small amount of iodine.
As the specific example of above-mentioned Alkoxymagnesium halides, methoxy magnesium chloride, ethyoxyl magnesium chloride, the third oxygen can be enumerated
Base magnesium chloride, butoxy magnesium chloride etc., preferred ethyoxyl magnesium chloride.The preparation method of the alkoxy magnesium compound, can be by
Prepared by method well known in the art, such as mix to prepare with purity titanium tetraethoxide and tetraethoxy-silicane by Grignard reagent butylmagnesium chloride
Ethyoxyl magnesium chloride.
The inert diluent that the formation of the mother solution in said method one is used can using hexane, heptane, octane, decane,
At least one in benzene, toluene and dimethylbenzene.The consumption of each composition that the formation of mother solution is used, in terms of every mole of magnesium, titanizing
Usage amount 0.5-100 mole of compound, preferably 1-50 mole；The usage amount of inert diluent is usually 0.5-100 mole, excellent
Elect 1-50 mole as；The total amount of electronic donor compound capable is usually 0.005-10 mole, preferably 0.01-1 mole.The shape of mother solution
Into when each component Contact Temperature be usually -40～200 DEG C, preferably -20～150 DEG C；It is usually 1 point time of contact
Clock -20 hours, preferably -8 hours 5 minutes.
In methods described one, in the titanium processing procedure, use alternative addition in the solution containing titanium tetrachloride lazy
Property diluent, the such as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene；In the titanium processing procedure,
The consumption containing each composition in titanium tetrachloride solution is used, in terms of every mole of magnesium, usage amount 0.5-100 mole of titanium compound,
Preferably 1-50 mole；The usage amount of inert diluent is usually 0-100 mole, preferably 0-50 mole；Titanium number of processes is
It is 0-10 time, preferred 1-5 time.In the titanium processing procedure, alternative adds above-mentioned electronic donor compound capable, wherein interior electron
Body consumption is usually 0.005-10 mole, preferably 0.01-1 mole.The titanium treatment temperature is usually 0～200 DEG C, preferably
30～150 DEG C；It is usually -20 hours 1 minute, preferably -6 hours 5 minutes time of contact.
Method two, by magnesium dihalide be dissolved in organic epoxy compound thing, organic phosphorus compound, aliphatic alcohols compound with it is lazy
Property diluent composition dicyandiamide solution in, formed homogeneous solution after with above-mentioned titanium compound, electron donor compound haptoreaction,
In the presence of precipitation additive, solidss are separated out, form mother solution；Mother solution is filtered, gained solid matter is suspended in containing titanium tetrachloride
Solution in carry out contact process, hereinafter known as titanium is processed；Then Jing is filtered, and washing can be prepared by the catalyst of the present invention and consolidate
Body component.
Precipitation additive used in method two is not particularly limited, as long as solid particle can be made to separate out molding.Can
Have with the example enumerated：At least one in organic acid anhydride, organic acid, ester, ether and ketone.The specific example of the organic acid anhydride can
Think at least one in acetic anhydride, phthalic anhydride, succinic anhydride and maleic anhydride etc., the organic acid it is concrete
Example can be at least one in acetic acid, propanoic acid, butanoic acid, acrylic acid and methacrylic acid etc., and the specific example of the ester can
Think dibutyl phthalate, 2,4-PD dibenzoate, 3- ethyls -2,4-PD dibenzoate, 2,3- bis-
Isopropyl -1,4- butanediol dibenzoates, 3,5- heptandiols dibenzoate and 4- ethyl -3,5- heptandiol dibenzoates
In at least one, the specific example of the ether can be methyl ether, ether, propyl ether, butyl ether, amyl ether, 2- isopropyl -2- isopentyl
Dimethoxy propane and 9,9-（Dimethoxy methyl）At least one in fluorenes, the ketone can be acetone, butanone and benzophenone
In at least one.
In method two, the organic epoxy compound thing for using can be selected from oxirane, expoxy propane, epoxy fourth
In alkane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether etc.
At least one, preferred epoxychloropropane.The organic phosphorus compound for using can be the hydrocarbyl carbonate of orthophosphoric acid or phosphorous acid or
Halogenated hydrocarbons base ester, the specific example of the organic phosphorus compound can be enumerated：Orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid
Tributyl, orthophosphoric acid triphenylmethyl methacrylate, NSC 6513, NSC 5284, tributyl phosphite or phosphorous acid benzene methyl etc., it is excellent
Select orthophosphoric acid tributyl.The aliphatic alcohols compound that uses can be the straight or branched alkane unitary of carbon number 1-20
Or multi-alcohol, the straight or branched unitary fatty alcohol of preferred carbon number 1-10, specific example can enumerate：Methanol, second
Alcohol, propanol, isopropanol, butanol, isobutanol, amylalcohol, hexanol, enanthol,（2- ethyls）Hexyl alcohol, capryl alcohol, nonyl alcohol, decanol etc., it is excellent
Choosing（2- ethyls）Hexyl alcohol.
In method two, the inert diluent used in mother solution is formed can adopt hexane, heptane, octane, decane, benzene, first
At least one of benzene and dimethylbenzene.The consumption of each composition used in mother solution formation, in terms of every mole of magnesium halide, organic epoxidation
Compound can be 0.2-10 mole, preferably 0.5-4 mole；Organic phosphorus compound can be 0.1-3 mole, preferably 0.3-
1.5 mole；Fat alcohol compound can be 0.2-10 mole, preferably 0.5-3 mole；Titanium compound can rub for 0.5-20
You, preferably 5-15 mole；Precipitation component is helped to be 0.01-0.3 mole, preferably 0.02-0.2 mole；Electron donor
Compound total amount can be 0-10 mole, preferably 0.02-0.3 mole.The Contact Temperature of each component leads to during the formation of mother solution
It is often -40～200 DEG C, preferably -20～150 DEG C；It is usually -20 hours 1 minute, preferably -8 hours 5 minutes time of contact.
In method two, in the titanium processing procedure, use alternative addition inertia in the solution containing titanium tetrachloride dilute
Release agent, the such as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In the titanium processing procedure, made
With the consumption containing each composition in titanium tetrachloride solution, in terms of every mole of magnesium, usage amount 0.5-100 mole of titanium compound, preferably
For 1-50 mole；The usage amount of inert diluent is usually 0-100 mole, preferably 0-50 mole.The titanium number of processes is
It is 0-10 time, preferred 1-5 time.In the titanium processing procedure, alternative adds above-mentioned electronic donor compound capable, wherein interior electron
Body consumption is usually 0.005-10 mole, preferably 0.01-1 mole.The titanium treatment temperature is usually 0～200 DEG C, preferably
30～150 DEG C；It is usually -20 hours 1 minute, preferably -6 hours 5 minutes time of contact.
Method three, the alcohol adducts of magnesium dihalide is suspended in inert diluent and forms suspension, then by the suspension
Solidss dispersion, hereinafter known as mother solution are contacted to obtain with above-mentioned titanium compound, internal electron donor mixing.By mother solution mistake
Filter, gained solid matter is suspended in the solution containing titanium tetrachloride carries out contact process, and hereinafter known as titanium is processed；Then pass through
Filter, washing can be prepared by the catalyst solid constituent of the present invention.
In method three, the alcohol adducts of the magnesium dihalide can be obtained by the following method：Not miscible with adduct
Atent solvent（Such as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene）In the presence of, by alcohol（As methanol, ethanol, third
Alcohol or isopropanol etc.）Emulsion is mixed to form with magnesium halide, makes the rapid chilling dispersion of the emulsion, gained spheroidal particle be dihalide
The alcohol adducts of magnesium.
In said method three, the inert diluent that the formation of mother solution is used can using hexane, heptane, octane, decane,
At least one in benzene, toluene and dimethylbenzene.The consumption of each composition that the formation of mother solution is used, in terms of every mole of magnesium, titanizing
Usage amount 0.5-100 mole of compound, preferably 1-50 mole；The usage amount of inert diluent is usually 0.5-100 mole, excellent
Elect 1-50 mole as；The total amount of electronic donor compound capable is usually 0.005-10 mole, preferably 0.01-1 mole.The shape of mother solution
Into when each component Contact Temperature be usually -40～200 DEG C, preferably -20～150 DEG C；It is usually 1 point time of contact
Clock -20 hours, preferably -8 hours 5 minutes.
In method three, in the titanium processing procedure, use alternative addition inertia in the solution containing titanium tetrachloride dilute
Release agent, the such as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In titanium processing procedure, use and contain
The consumption of each composition in titanium tetrachloride solution, in terms of every mole of magnesium, usage amount 0.5-100 mole of titanium compound, preferably 1-
50 moles；The usage amount of inert diluent is usually 0-100 mole, preferably 0-50 mole.Titanium number of processes is 0-10 time, excellent
Select 1-5 time.In titanium processing procedure, alternative adds above-mentioned electronic donor compound capable, wherein internal electron donor consumption to be usually
0.005-10 mole, preferably 0.01-1 mole.Titanium treatment temperature is usually 0～200 DEG C, preferably 30～150 DEG C；During contact
Between be usually -20 hours 1 minute, preferably -6 hours 5 minutes.
According to another aspect of the present invention, there is provided a kind of catalyst for olefines polymerizing, it includes following components
Product：
A. above-mentioned catalyst solid constituent；
B. organo-aluminum compound；
C. optionally, external donor compound.
Can be olefinic polymerization as the organo-aluminum compound of promoter according to olefin polymerization catalysis of the present invention
The organo-aluminum compound of the conventional various promoters that can act as Ziegler-natta catalyst in field.It is preferred that described have
Machine aluminium compound is formula AlR'n'X'3-n'Shown organo-aluminum compound, wherein, R' is selected from hydrogen, C1-C20Alkyl and C6-
C20Aryl；X' is halogen, and n' is the integer of 1-3.
In above-mentioned catalyst, described organo-aluminum compound preferably is selected from least one in following compound：Trimethyl aluminium,
Triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chlorine two
At least one in aluminium isobutyl, sesquialter ethylmercury chloride aluminum and ethyl aluminum dichloride.More preferably triethyl aluminum and/or triisobutyl
Aluminum.
In above-mentioned catalyst, the consumption of the organo-aluminum compound can be the conventional amount used of this area.Usually, it is described
The mol ratio of the titanium in the aluminum in organo-aluminum compound and the catalyst is 5-5000：1；Preferably 20-1000：1；More preferably
For 50-500：1.
It is described to optionally mean that the product that the catalyst include component a and b in above-mentioned catalyst, also may be used
Product comprising component a, b and c.According to olefin polymerization catalysis of the present invention, the external electron donor component can be with
For various external electron donors known in the industry, it is not particularly limited.
In above-mentioned catalyst, the external electron donor is preferably general formula R1″m″R2″n″Si(OR3″)4-m″-n″Shown organosilicon
Compound, in formula, R1" and R2" it is identical or different, it is each independently selected from：Halogen, hydrogen atom, C1-C20Alkyl, C3-C20's
Cycloalkyl, C6-C20Aryl and C1-C20Haloalkyl；R3" it is selected from C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20's
Aryl and C1-C20Haloalkyl；M " and n " is respectively the integer of 0-3, and m "+n "<4.Preferably, the organo-silicon compound
At least one in following compound：Trimethylmethoxysilane, diisopropyl dimethoxy silane, diisobutyl diformazan
TMOS, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxy silicon
Alkane, t-butylethyl dimethoxysilane, tert-butyl group propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, ring
Hexyl methyl dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopenta first
Base dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxy
It is base silane, double（2- methylcyclopentyls）Dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, benzene
Ethyl triethoxy silicane alkane, MTMS, MTES, ethyl trimethoxy silane, propyl group trimethoxy
Base silane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silicon
It is alkane, butyl triethoxysilane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, different
Amyltrimethoxysilane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, two
Diethylamino phenyl TMOS, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyl
Triethoxysilane, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes；These organo-silicon compound can be respectively
It is used alone, it is also possible to be applied in combination two or more.
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.In preferred feelings
Under condition, the mol ratio of aluminum and the external donor compound in the organo-aluminum compound is 0.1-500：1, preferred 1-
300：1, more preferably 3-100：1.I.e. when the external donor compound selects organo-silicon compound, the organo-aluminium chemical combination
Thing is calculated as 0.1 with the mol ratio of organo-silicon compound with aluminum/silicon:1-500:1, preferably 1:1-300:1, more preferably 3:1-100:1.
According to another aspect of the present invention, there is provided a kind of olefine polymerizing process, the alkene is in above-mentioned catalyst
It is polymerized in the presence of component or above-mentioned catalyst.
Olefine polymerizing process of the invention, it can be not only used for the homopolymerization of alkene, it can also be used to the copolymerization of alkene.
According to the present invention, the formula of the alkene is CH2=CHR, R are hydrogen or C1-C12Alkyl, preferably hydrogen or C1-
C6Alkyl.At least one being preferably selected from such as the alkene in following compound：Ethylene, propylene, 1- n-butenes, 1- positive penta
Alkene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene；At least one being more preferably selected from ethylene, propylene and 1-butylene.
According to olefine polymerizing process of the present invention, the olefin polymerization conditions are 0-150 for the temperature of olefinic polymerization
DEG C, preferred 60-130 DEG C；Time be 0.1-5 hours, preferred 0.5-4 hours, pressure is 0.01-10MPa, preferably 0.5-
5MPa.The consumption of catalyst can be the consumption of the various catalyst of prior art.
Catalyst according to the invention component and catalyst are high, three-dimensional with polymerization activity when it is used for olefinic polymerization
The advantages of isotacticity height of the polymer that capacity of orientation is good, obtain and high melt index.
According to the present invention, using the formula of new structure（I）What shown compound was obtained as internal electron donor compound
Catalyst, phthalate is adopted for internal electron donor with the most frequently used in prior art（It has been found to be unfavorable for people
Fertility）Compare, with higher safety, and significantly improve the melt index of polymer（Mean to improve
The hydrogen regulation performance of catalyst）.When catalyst according to the invention is used for olefinic polymerization, with polymerization activity is suitable and stereotaxises
The good advantage of ability, and the polymer for obtaining has high, the higher melt index of preferable isotacticity and bulk density, is conducive to
The exploitation of different trade mark polymer.Especially there is high melt index, it is meant that catalyst has good hydrogen regulation performance, fit
In the exploitation of specific acrylic resin.According to the new catalyst that the present invention is provided, with excellent combination property, with width
Wide application prospect.
Specific embodiment
Example given below is used to further illustrate the present invention, but does not constitute any limitation of the invention.
Method of testing：
1st, the Ti content in catalyst：Tested according to 721 spectrophotometers.
2nd, catalyst grain size distribution：Measured according to the normal hexane dispersant laser diffractometry of Malvern 2000.
3rd, the measure of melt index：Determined according to GB/T3682-2000.
4th, polymer isotacticity is determined using heptane extraction process：2 grams of dry polymer samples, are placed in extractor with boiling
After rising heptane extracting 6 hours, by residue drying to the polymer weight obtained by constant weight（g）With 2（g）Ratio be isotactic
Degree.
5、1H NMR are determined：Using Bruker dmx nmr determinations（300MHz, solvent C DCl3, internal standard TMS, survey
Constant temperature degree 300K）.
6th, internal electron donor content uses Agilent7890Series gas Chromatographic Determination.
First, synthesis example：
The synthesis of double (the methoxymethylene) -1,3- Propylene Glycol of 2,2-：
1）The synthesis of 2- ((2- phenyl) -1,3- dioxocyclohex bases) -1,3- Propylene Glycol：
54.4g tetramethylolmethanes（Mw=136.15,0.4mol）It is dissolved in 500mL water.40 DEG C are warming up to, 42.4g benzene first is added
Aldehyde（Mw=106,0.4mol）With 2mL concentrated hydrochloric acid, stirring reaction 6 hours.Reaction system stands overnight.Sucking filtration, filter cake is added
800mL water and 0.5g potassium carbonate, stir rising temperature for dissolving, crystallisation by cooling.Filter, obtain the 75 DEG C of dryings of crude product vacuum.Crude product toluene
Recrystallization, final product 72.6g, yield 81%.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.56(s,4H,-C(CH2OH)2),3.76,3.79(s,4H,-C
(CH2O)2CH-),5.44(s,1H,phCH-),7.37-7.39(m,5H,C6H5CH-)。
2）The synthesis of 2- ((2- phenyl) -1,3- dioxocyclohex bases) -1,3- dimethoxy propanes：
20g60wt%NaH（Mw=24.0,0.5mol）In being scattered in 200mL dry tetrahydrofurans.Take 44.8g2- ((2- benzene
Base) -1,3- dioxocyclohex bases) -1,3- Propylene Glycol（Mw=224.25,0.2mol）In being dissolved in 400mL dry tetrahydrofurans, room temperature
In the suspension of lower instillation NaH, 25-30 DEG C is continued to react 2 hours after completion of dropping.10 DEG C are cooled to, Deca 42.6mol sulphuric acid
Dimethyl ester（0.45mol）, add rear room temperature and continue to react 4 hours, back flow reaction 4 hours.Stopped reaction, Deca 100mL water.Have
Machine is mutually washed 2 times, is dried, and is filtered.Solvent is evaporated off, product about 46.3g, yield 92% are collected in vacuum distillation.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.30(s,6H,-C(CH2OCH3)2),3.70(s,4H,-C
(CH2O-)2),3.86,3.88(s,4H,-C(CH2OCH3)2),7.37-7.47(m,5H,C6H5CH-)。
3）The synthesis of double (the methoxymethylene) -1,3- Propylene Glycol of 2,2-：
High-pressure reactor（Nitrogen displacement）Middle addition 300mL acetic acid, 5g10wt%Pd-C.50g2- ((2- phenyl) -1,3- two
Oxygen cyclohexyl) -1,3- dimethoxy propanes are dissolved in 100mL acetic acid, add in high-pressure reactor.It is filled with hydrogen（5atm）, rise
Temperature to 40 DEG C are reacted 24 hours.Terminate reaction, filtrate rotation removes solvent, adds 120mL20%NaOH solution, temperature rising reflux 2 hours.
Dichloromethane is extracted.Merge organic faciess, be dried, filter, be spin-dried for solvent, obtain product 26.4g, yield 81%.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.34(s,6H,-C(CH2OCH3)2),3.44(s,4H,-C
(CH2OH)2),3.64,3.66(s,4H,-C(CH2OCH3)2)。
Compound 1：The synthesis of double (acetoxyl group the methylene) -1,3- dimethoxy propanes of 2,2-：
Double (the methoxymethylene) -1,3-PDs of 24g (145mmol) 2,2-, 38g, 52.2mL (376mmol) triethylamine
Mixing, in adding the chloroform that 150mL is dried.29.52g, 26.73mL (376mmol) chloroacetic chloride is dissolved in the three of 90mL dryings
In chloromethanes, instill wherein, keeping temperature is stable below 5 DEG C during Deca, completion of dropping rises to 30 DEG C and reacts 2 hours,
It is warming up to 50 DEG C to react 4 hours.Reaction terminates, and is spin-dried for solvent, adds 250mL ethyl acetate, solids removed by filtration.Add
300mL water, point liquid, water is extracted twice using ethyl acetate, merges organic faciess, and anhydrous magnesium sulfate is dried, and filters, and is spin-dried for molten
Agent, vacuum distillation obtains final product 30.1g, yield 83%.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):2.12(s,6H,-OCOCH3),3.27(s,6H,-OCH3),
3.82(s,4H,-CH2OCH3),4.03(s,4H,-CH2OCOCH3)。
Compound 2：The synthesis of double (isobutyl acyloxy the methylene) -1,3- dimethoxy propanes of 2,2-：
Double (the methoxymethylene) -1,3-PDs of 20g (122mmol) 2,2-, 30.36g (300mmol) triethylamine is mixed
Close, the dichloromethane for adding 150mL to be dried.31.2g (292.7mmol) isobutyryl chloride is dissolved in the dichloromethane of 100mL dryings,
Instill wherein, keeping temperature is stable below 5 DEG C during Deca, and completion of dropping is warmed to room temperature and is stirred overnight naturally.Reaction knot
Beam, adds 300mL water, point liquid, and water is mutually extracted three times using dichloromethane, merges organic faciess, and anhydrous magnesium sulfate is dried, and filters,
Solvent is spin-dried for, vacuum distillation obtains final product 29.2g, yield 79%.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):1.16-1.25(d,12H,(-COCH(CH3)2)),2.51-
2.60(m,2H,(-COCH(CH3)2)),3.30(s,6H,-OCH3),3.36(s,4H,-CH2OCH3),4.09(s,4H,-
CH2OCOCH2(CH3)2)。
Compound 3：The synthesis of double (benzoxy the methylene) -1,3- dimethoxy propanes of 2,2-：
Double (the methoxymethylene) -1,3-PDs of 20g (122mmol) 2,2-, 30.36g (300mmol) triethylamine is mixed
Close, the dichloromethane for adding 120mL to be dried.41.1g (292.7mmol) Benzenecarbonyl chloride. is dissolved in the dichloromethane of 150mL dryings,
Instill wherein, keeping temperature is stable below 5 DEG C during Deca, and completion of dropping is warmed to room temperature and is stirred overnight naturally.Reaction knot
Beam, adds 300mL water, point liquid, and water is mutually extracted three times using dichloromethane, merges organic faciess, and anhydrous magnesium sulfate is dried, and filters,
Solvent is spin-dried for, vacuum distillation obtains final product 33.1g, yield 73%.
1H NMR(CDCl3/TMS,300MHz)δ(ppm):3.31(s,6H,-OCH3),3.54(s,4H,-CH2OCH3),
4.49(s,4H,-CH2OCOC6H5),7.34-7.42(m,4H,-C6H5),7.52-7.61(m,2H,-C6H5),7.7.96-8.08
(m,4H,-C6H5)。
Two：Application examples
Embodiment 1：
The preparation of alkoxyl magnesium
It is prepared by alkoxyl magnesium：In the 1L reactors with agitator, reflux condensing tube, thermometer and burette, nitrogen is used
After gas is sufficiently displaced from, ethanol 550mL, isopropanol 10mL, iodine 0.68g dissolving are added in reactor.Open and risen after stirring
Temperature, until it reaches the reflux temperature of reaction system.Then magnesium powder 32g is gradually added；React to it there is no longer hydrogen discharge.So
After washed, filtered and be dried, obtain bulk density 0.25g/cm3, mean diameter（D50）47.0 μm of alkoxyl magnesium 147g.
The preparation of ingredient of solid catalyst：
Take alkoxyl magnesium carrier 10g obtained above, toluene 50mL and 2.5g internal electron donor（The compound of above-mentioned preparation
1）, it is configured to suspension；In the reactor of 300mL of displacement is repeated through high pure nitrogen, toluene 40mL and four chlorinations are added
Titanium 60mL, then adds the suspension for preparing in kettle, is warming up to 80 DEG C, and constant temperature is continuously heating to 115 DEG C after 1 hour, perseverance
Temperature is after 2 hours by liquid（Mother solution）Filter pressing is clean.The mixed liquor of addition toluene 90mL and titanium tetrachloride 60mL is warming up to 110 DEG C and stirs
Mix process 1 hour（Titanium process）, by liquid（Mother solution）Filter pressing is clean, adds the mixing of toluene 120mL and titanium tetrachloride 30mL
Liquid is warming up to 110 DEG C of stir process 2 hours（Titanium process）, liquid is filtered off, the solid of gained is washed at 55 DEG C with normal hexane 150mL
3 times, washed once with normal hexane in room temperature, filter off liquid and be dried, obtain final product the catalytic component 1-3 of the present invention.
Propylene polymerization
In 5 liters of autoclaves, Jing after gas-phase propene is sufficiently displaced from, add at room temperature 5 milliliters of triethyl aluminums oneself
Alkane solution (concentration of triethyl aluminum be 0.5mmol/mL), l milliliter Cyclohexyl Methyl Dimethoxysilanes (CHMMS) hexane it is molten
Liquid (concentration of CHMMS is 0.10mmol/mL), 10mL anhydrous hexanes and the above-mentioned ingredients of solid catalyst for preparing of 10mg.
Autoclave is closed, the liquid propene that 4.5 standards rise hydrogen and 2L is introduced；Under agitation temperature is risen to into 70 DEG C in 10 minutes.
Polyreaction stops stirring after 1 hour at 70 DEG C, removes unpolymerized propylene monomer, collected polymer.Catalyst activity passes through
To polymer quality (Kg) with the ratio of the catalyst quality (g) for using calculating.
Embodiment 2-3：
Step is simply respectively changed to internal electron donor during ingredient of solid catalyst preparation with embodiment 1
State the compound 2 and 3 of preparation, consumption 2.5g.
Comparative example 1：
Internal electron donor is simply changed to adjacent benzene two by step with embodiment 1 during ingredient of solid catalyst preparation
Formic acid di-n-butyl（DNBP）, consumption 2.5g.
The performance of the catalyst of table 1
In table, contentaRefer to the mass percent of internal electron donor in catalyst.
As can be seen from Table 1, using comprising ad hoc structure internal electron donor of the present invention（The formula of new structure
Compound shown in I）The catalyst for preparing of catalytic component, with the most frequently used containing the positive fourth of phthalic acid two in prior art
Comparing for ester, not only increases the safety of catalyst, and significantly improves the melt index of polymer（Mean to improve and urge
The hydrogen regulation performance of agent）.When catalyst according to the invention is used for olefinic polymerization, with suitable polymerization activity and stereotaxises
The good advantage of ability, and the polymer for obtaining has high, the higher melt index of preferable isotacticity and bulk density.Especially
With high melt index, it is meant that catalyst has good hydrogen regulation performance, the exploitation of specific acrylic resin is suitable to.According to
The new catalyst that the present invention is provided, with excellent combination property, with broad application prospect.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.By regulation the present invention can be made within the scope of the claims
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this
It is bright to can be extended to other all methods and applications with identical function.
Claims (19)
1. a kind of catalyst solid constituent for olefinic polymerization, including the compound shown in titanium, magnesium, halogen and Formulas I,
Compound shown in the Formulas I is double (different selected from double (acetoxyl group the methylene) -1,3- dimethoxy propanes of 2,2-, 2,2-
Butyryl acyloxy methylene) -1,3- dimethoxy propanes, double (benzoxy the methylene) -1,3- dimethoxy propanes of 2,2-.
2. catalyst solid constituent according to claim 1, it is characterised in that the content of the titanium is 1.0-8.0wt%；
The content of the magnesium is 10-70wt%；The content of the halogen is 20-85wt%；Content 2- of the compound shown in the Formulas I
30wt%.
3. catalyst solid constituent according to claim 2, it is characterised in that the content of the titanium is 1.6-6.0wt%；
The content of the magnesium is 15-40wt%；The content of the halogen is 30-80%；Content 3- of the compound shown in the Formulas I
20wt%.
4. catalyst solid constituent according to claim 1, it is characterised in that the catalyst solid constituent includes magnesium
Compound shown in compound, titanium compound and Formulas I product in a solvent.
5. catalyst solid constituent according to claim 4, it is characterised in that the magnesium compound is selected from formula M gR4R5
Shown magnesium compound, formula M gR4R5·pH2The hydrate and formula M gR of the magnesium compound shown in O4R5·qR6Shown in OH
Magnesium compound alcohol adducts, in formula, R4And R5It is each independently selected from halogen, C1-C8Straight or branched alkoxyl
And C1-C8Straight or branched alkyl；P and q are separately selected from 0.1-6；R6For C1-C18Alkyl.
6. catalyst solid constituent according to claim 5, it is characterised in that p and q are separately selected from 2-3.5；R6
For C1-C8Alkyl.
7. catalyst solid constituent according to claim 6, it is characterised in that R6Selected from methyl, ethyl, n-pro-pyl and different
Propyl group.
8. the catalyst solid constituent according to claim 4 or 5, it is characterised in that the formula of the titanium compound is TiXm
(OR7)4-m, in formula, X is halogen, R7For C1-C20Alkyl, m for 0-4 integer.
9. catalyst solid constituent according to claim 8, it is characterised in that R7For C1-C5Alkyl.
10. catalyst solid constituent according to claim 8, it is characterised in that the titanium compound is titanium tetrachloride.
A kind of 11. catalyst for olefinic polymerization, it includes the product of following components：
A. the catalyst solid constituent in claim 1-10 described in any one；
B. organo-aluminum compound；
C. optionally, external donor compound.
12. according to claim 11 catalyst, it is characterised in that
B. organo-aluminum compound is formula AlR'n'X'3-n'Shown organo-aluminum compound, wherein, R' is selected from hydrogen, C1-C20Alkane
Base and C6-C20Aryl；X' is halogen, and n' is the integer of 1-3；
C. external donor compound is general formula R1”m”R2”n”Si(OR3”)4-m”-n”Shown organo-silicon compound, in formula, R1" and
R2" identical or different, it is each independently selected from：Halogen, hydrogen atom, C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Virtue
Base and C1-C20Haloalkyl；R3" it is selected from C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl and C1-C20Halo
Alkyl；M " and n " is respectively the integer of 0-3, and m "+n "<4.
13. according to claim 11 catalyst, it is characterised in that the organo-aluminum compound and catalyst solid constituent
Mol ratio is calculated as 5 with aluminum/titanium:1-5000:1；The mol ratio of aluminum and external donor compound in the organo-aluminum compound
For 0.1:1-500:1.
14. according to claim 13 catalyst, it is characterised in that the organo-aluminum compound and catalyst solid constituent
Mol ratio is calculated as 20 with aluminum/titanium:1-1000:1；The mol ratio of aluminum and external donor compound in the organo-aluminum compound
For 1:1-300:1.
15. according to claim 14 catalyst, it is characterised in that the organo-aluminum compound and catalyst solid constituent
Mol ratio is calculated as 50 with aluminum/titanium:1-500:1；The mol ratio of aluminum and external donor compound in the organo-aluminum compound
For 3:1-100:1.
A kind of 16. olefine polymerizing process, the alkene in claim 1-10 catalyst solid constituent described in any one or
It is polymerized in the presence of catalyst described in any one in claim 11-15.
17. methods according to claim 16, it is characterised in that the formula of the alkene is CH2=CHR, R are hydrogen or C1-
C12Alkyl.
18. methods according to claim 17, it is characterised in that the alkene is selected from ethylene, propylene, 1- n-butenes, 1-
N-pentene, 1- n-hexylenes, the positive octenes of 1- and 4-methyl-1-pentene, R is hydrogen or C1-C6Alkyl.
19. methods according to claim 18, it is characterised in that the alkene is selected from ethylene, propylene and 1-butylene.
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| US6118019A (en) * | 1994-09-28 | 2000-09-12 | Showa Denko K.K. | 3-alkoxypropionic ester derivative |
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| US6118019A (en) * | 1994-09-28 | 2000-09-12 | Showa Denko K.K. | 3-alkoxypropionic ester derivative |
| CN1292800A (en) * | 1998-11-04 | 2001-04-25 | 蒙特尔技术有限公司 | Components and catalysts for polymerization of olefins |
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